JPH01123784A - Recording material - Google Patents

Abstract

PURPOSE:To contrive higher color forming properties, raw preservability and stability of developed color images, by using a compound of a specified formula as an electron-acceptive compound. CONSTITUTION:A compound of the formula, wherein R is a divalent group comprising at least one aromatic ring, and each of R1-R4 is hydrogen, a halogen, alkyl, alkoxyl, aryl, aryloxyl, alkoxycarbonyl, acyl or hydroxyl, is used as an electron-acceptive compound. An electron-donative colorless dye for giving a colored substance by making contact with the electron-acceptive compound may be any of various compounds such as leuco compounds and triphenylmethane phthalide compound. The amounts of the electron-donative colorless dye and the electron-acceptive compound can be appropriately selected depending on the desired coating thickness, the form of a pressure sensitive copying paper, the preparation method of capsules or other conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and more particularly to a recording material with improved color development, shelf life, and stability of colored images.

(Prior Art) Recording materials using an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, thermal paper, light-sensitive pressure-sensitive paper, electrically conductive thermal paper, and the like. For example, British patents λ, l
≠0. No. 1A4, U.S. Patent Office.

pro, oss No. II, 1IJt, No. 920, Special Publication Show 1. o-23, ri2ko, JP-A-17-17-7ri.

No. 134, 40-/23,! ! He is familiar with issues such as To-L Co. J and J-J-7.

The performance that a recording material should have is (I) sufficient color density and color development sensitivity, (2) no fogging, (3) sufficient fastness of color body, and (4) color development. Appropriate hue and suitability for copying machine, (5) 8/N
(6) The chemical resistance of the color former is sufficient, and research is being conducted to improve these properties, especially in recent years as recording systems have become faster and requirements have become more diverse. .

There have been attempts to use alkylene-linked thiohydroquinone derivatives as electron-accepting compounds to improve the chemical resistance of color formers, but while this certainly improves the chemical resistance, it also reduces the water resistance of color formers. However, it also has drawbacks such as powder blowing over time, and improvements in these problems are desired.

We have discovered that the properties of recording materials can be greatly improved by incorporating unique ideas into electron-accepting compounds. As will be described later, its properties are significantly improved by using it in combination with a specific amide compound and/or ether compound.

(Objective of the Invention) Therefore, the object of the present invention is to provide a recording material having good color development properties, shelf life, and stability of colored images.

(Structure of the Invention) The object of the present invention is to prepare an electron-accepting compound of the following general formula (
This was achieved by developing a recording material using the compound represented by I).

In the above formula, B is a divalent group containing at least one aromatic ring,
R represents a hydrogen atom, an atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an acyl group, or a hydroxy group.

Among the substituents represented by R in the above formula, those having 6 to 30 carbon atoms are preferable, and these are -〇-1-S-1-CO-1
It may have a linking group such as -OCO-1-CO□-1.

Further, the phosphor may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, or an aryl group.

A typical preferred example is -Cn H2m -11,n
, m represents an integer from 1 to 30.

As a specific example, in formula (I), -8-R-8- is preferably at the para position with respect to -○H from the viewpoint of raw material availability.

Among the substituents represented by ~R4, a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having a carbon atom number of /-/-, an alkoxy group, an alkoxycarbonyl group, an acyl group,
Aryl groups and aryloxy groups having J-/co carbon atoms are preferred.

Specific examples of R to R4 include hydrogen atom, chlorine atom, and bromine atom. Examples include hydroxy group, methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, methoxycarbonyl group, phenyl group, and allyl group.

A synthesis example is shown below (I) α,α'-bis(≠-hydroxyphenylthio)-p-xylene In a three-necked flask of JOOrd, 0.00% of thiohydroquinone is added.
2M, weigh out 100d of dimethylacetamide,
While cooling with ice and stirring, 0.2 ml of at% caustic soda water was added dropwise. Raise the internal temperature to JO″C and p-xylylene dichloride o
, tM was added in three parts, and the internal temperature was increased! Stir at O"C for 3 hours. Pour the reaction mixture into water and make acidic with hydrochloric acid, and crystals will precipitate. The crystals are separated from F and washed with water and acetone. The target product is pale yellowish white crystals, melting point. -1t-r
``obtained as c.

(2) α,αI-bis(≠-hydroxyphenylthio)-o-xylene & release (I) Using O-xylylene dichloride instead of p--+silylene dichloride, the reaction is carried out in the same manner. The obtained crystals are recrystallized from chloroform to obtain the desired product as pale yellowish white crystals with a melting point of /jO-10C.

Next, specific examples of the electron-accepting compound of the present invention will be shown, but the present invention is not limited to these specific examples.

Next, the electron-donating colorless dye that gives a colored product when it comes into contact with the above-mentioned electron-accepting compound will be described.

Electron-donating colorless dyes include well-known leuco compounds, triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leuco auramine compounds, and rhodamine lactam compounds.・Various compounds include compounds, triphenylmethane compounds, triazene compounds, and spiropyran compounds.

Specific examples of these various existing colorless dyes, such as phthalides, are U.S. Reissue Patent Co. J, No. 02≠, U.S. Pat.
．． Dub No. 1,111, 3.4L/, No. 112, 3
．． 4! Specific examples of fluorans are U.S. Pat. No. J, 4217.1.
07 issue, same J, t core, 7t7 issue, same j, 4g/, 0/
/ issue, same 3. Hirotko.

No. t, 3. tlrl, Jri No. 0, same 3. P coo,
zio issue, same 3. the law of nature! the law of nature,! Specific examples of spiropyrans are described in US Pat. No. 31/7/, Irot, etc.

Some examples of colorless dyes include triarylmethane compounds such as 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide and 3,3-bis(p-dimethylaminophthalide).
-diethylaminophenyl)phthalide, 3-(4t-diethylamino-coethoxyphenyl)-J-(/-n
-octyl-2-methylindol-3-yl)phthalide, 3-(U-diethylaminocoethoxyphenyl)-s-(l-n-octyl-2-methylindole-
3-yl)-μm or -7-azaphthalide, etc., as diphenylmethane compounds, ≠, 4t'-bis-dimethylaminobenzhydryl beyzyl ether, N-
Halophenyl-leucoauramine, N-2, Hiroshi, j
-) +7 Chlorophenylleucoolamine etc., and xanthine compounds include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, colabenzylamino-t-diethylaminofluoran ,−
-anilino-t-diethylaminofluorane, co-anilino-3-methyl-t-diethylaminofluorane, -
-anilino 3-methyl-&-N-cyclohexyl-N
-Methylaminofluorane, co-coroanilino-
4-diethylaminofluorane, co-m-) salamino-3-methyl- to one-diethylaminofluorane/,! , &
-dibutoxyfluorane, -monooctylureido-6-
Dinitylaminofluoran, λ-Regihexadecylamino-6-diethylaminofluoran , no β-phenoxyethoxyethylamino-3-
Chloro-6-diethylaminofluorane, co-anilino 3-methyl-t-dibutylamino-j-methylfluoran, co-anilino 3-methyl-6-sioctylamino? -Methylfluoran, co-anilino 3-chloro-6-dinithylaminofluorane, co-anilino 3-
Methyl-4-N-β-pyridylethyl-N-ethylaminofluorane, 2-phenyl-G-diethylaminofluorane, co-anilino 3-methyl-J-N-ethyl-
N-inamylamine fluoran, co-anilino 3-
Methyl! -chloro-4-diethylaminofluorane,
-1-anilino-3-methyl-6-dinithylamine-7-
Meterfluorane, λ-anilino 3-7 dinokiter 6
-dibutylaminofluorane, -p-chloroanilino-3-ethoxy-j-N-ethyl-N-isoamylaminofluorane, 2-0-chloroanilino-t-p-butylanilinofluorane, -1anilino 3- Pentadecyl-t-diethylaminofluorane, -1anilino 3
-Ethyl-t-digtylaminofluorane, co-anilino 3-methyl-3', j'-dichlorofluoran, co-toluidino 3-methyl-4-N-octyl-N
-isopropylamino-san',! '-dimethylaminofluorane/, noanilino-3-ethyl-4-N-ethyl-N-isoamylaminofluorane, --anilino-3
-Methyl-N-Ether-N-Teikobilidylpropylaminofluorane, -1anilino-3-chlorot
-N-Ether-N-ynylaminofluorane and the like are J', J'-bisdiethylamino-! -diethylaminospiro(isobenzo7ran-/,ri'-fluorene)-j-one 3/,1/-bisdimethylamino-! -dibutylaminospiro(inbenzofuran-/, P'-fluorene)-3-one, 3/
, j/-bisdibutylamino-yo-diethylaminospiro(inobe/cyfuran-7,ri'-fluorene)-3/
-on, 3/, 1. /-bis-N-ether-N-isoamylaminospiro(inbenzofuran=7.ri'-diphenoΦdiethylamino!-fluorene)-3-one, etc., but as thiazine compounds, pensoylleucomethylene blue, p -Nitrobenzoylleucomethylene blue, etc., and examples of spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, and 3°! '-Dichlorospiro-dinaphthothiapyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(J-methoxy-benzo)spiropyran,
Examples include 3-propyl-spiro-dibenzopyran, and it is desirable to use two or more of them in combination.

In addition to the above-mentioned compounds, examples of electron-accepting compounds that impart color upon contact with colorless dyes include common known compounds such as phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, and novolak resins. , metal-treated novolac resin, μ-tert-butylphenol, ≠-phenylphenol, x,2-bis(
≠-Hydroxyphenyl)propane, μ′-isopropylidene bis(co-methylphenol), /.

/-his-(3-chloro-μmm hydromphenyl)cyclohexane, /, l-bis(j-chloro-≠-hydroxyphenyl)-coethylbutane, ≠, tcrt-
Octylphenol, μ.

≠'-5ec-i teridendiphenol, p-chlorophenylphenol, 4<, 4t'-isopentylidene diphenol, μ'-methylcyclohexylidene diphenol, μ, ri'-dihydroxydiphenylsulfone, /9μm Bis-q'-hydroxycumylbenzene, /
, 3-bis-μ'-hydroxycumylbenzene, Hiroshi, 4
t'-thiobis(6-tert-butyl-3-methylphenol), ≠'-dihydroxy 3,3'-diallyldiphenyl sulfone, hydroquinone monobenzyl ether, ≠-hydroxybenzophenone 5.2. μm dihydroxybenzophenone, polyvinylbenzyloxycarbonylphenol 1.2,44.44'-trihydroxybensiphenone, J,! ', <4゜μ'-tetrahydraxybenzophenone, ≠-dimethyl hydroxyphthalate, Hiroshi-methyl hydroxybenzoate, co, France,
μ'-trihydroxydiphenylsulfone, t,z-bis-p-hydroxybenzoyloxyintane, /, A
-bis p-hydroxyphenoxybenzoic acid, ≠-tolyl hydroxybenzoate, Hiro-hydroxybenzoic acid α-phenylbenzyl ester, -hydrokey/phenylpropyl benzoate, 3-chloro-Hiro-hydroxybenzoic acid phenethyl, Hiro- p-chlorobenzyl hydroxybenzoate, p-meth+dibenzyl hydroxybenzoate,
l-hydroxybenzoic acid benzyl ester, μm hydroxybenzoic acid -m-70 lobenzyl ester, ≠-hydroxybenzoic acid β-phenethyl ester, ≠-hydroxy-2/, μ/-dimethyldiphenyl sulfone, β-
Phenethyl orselinate, ethyl orselinate, cinnamyl orselinate, orselic acid-〇-chlorophenoxyethyl ester, 0-ethylphenoxyethyl orselinate, phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate ,
x, 4t--) Hydroxybenzoic acid-β-3'-t-butyl-p/-hydroxybenzoic acid diphenoxyethyl ester/
-t-butyl-gu p-hydroxyphenylsulfonyloxybenzene, μ-N-benzylsulfamoylphenol, 2. It-dihydroxybenzoic acid-p-methylbenzyl ester, 21 μm dihydro 1'benzoic acid-β
-phenomodiethyl ester, co,4t-dihydroxy-6-methylbenzoic acid hensyl ester, bis-μm allyl hydroxyphenylacetate, ditolylthiourea, ≠
p/-Diacetyldiphenylthiourea, 3-phenylsalicylic acid,! -p-α-methylbenzyl-α-methylbenzylsalicylic acid, j-p-methoxyphenoxyethyloxysalicylic acid,! -Phenoxyethoxysalicylic acid, t-p-benzyl-α-methylbenzylsalicylic acid, 3-xylyl-j-(α.

α-dimethylbenzyl) salicylic acid, J,! −G (α
-methylbenzyl)salicylic acid, λ-human oxygen-
α-ethylbenzyl-J-su7)! Aromatic carboxylic acids such as acids; 3. ! - acids such as dicyclopentagenyl salicylic acid or zinc salts, p-hydroxybenzoic number β-p'
-methoxyphenoxybutyl ester, p-hydrobenzoic acid δ-phenoxybutyl ester 1.2.4A,
4-trihydroxybenzoic acid β-p-ethoxyphenoxyethyl ester, p-hydroxybenzoic acid β-phenoxyethoxyethyl ester, p-human 10xybenzoic acid-β-p-butoxyphenoxyisozolopyl ester, co-dihydroxy Benzoic acid β-p-methoxyphenoxyethoxyethyl ester, orcellic acid phenoxybutyl ether, β-resorcinic acid p-methoxyphenoxyethyl ether, orcellic acid β-p-methoxyphenoxyethoxyethyl ether, orcellic acid β-0-methoxy Phenoxyethyl ether, orcerin tolyloxyethyl ester, orcerin acid-β
-p-methoxyphenoxypropyl ester, β-resorcinic acid phenoxyethyl ether, β-resorcinic acid δ-p-methoxyphenoxybuter ester, -1-carboxy-1β-phenoxyethoxynaphthol, phenyl Organic color developers such as phenols such as phenol-formalin resin and para-glutylphenol acetylene resin, as well as polyvalent compounds such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel. metal salts, especially zinc salts,
Inorganic Shun, acid clay, activated clay, atta/zeta guide, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, zinc rhodan, zinc rhodan/benzylantipyrine complex, zinc chloride, iron stearate, naphthenic acid Cobalt, nickel peroxide, inorganic color developers such as ammonium nitrate, carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid, benzoylpropionic acid, benzoic acid, paratertiary butylbenzoic acid, phthalate One or more acids such as gallic acid may be used in combination with the electron-accepting compound of the present invention.

When these colorless dyes and electron-accepting compounds are applied to recording materials, they are used in the form of fine dispersions or fine droplets.

When used with pressure sensitive paper, U.S. Pat.
No. 0, same λ, 10! , ≠7/issue, same.

rot, at number, same 2. ! t4AI, Jtt issue, same, 7/λ, 107, same, 730, Hiro! 2.730, 4A77, J, 10J, Hiro O≠, 3,47/r, 2!0, 4A, 010゜o3
It can take various forms as described in prior patents such as No. R. Most commonly they consist of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

For a method of manufacturing capsules, see U.S. Patent 2.100.
, 4c77, λ, 10θ, a method using coacervation of a hydrophilic colloid sol described in art, British Patent No. 147,727, PjO, 14cj,
Same rF, No. 2644, Same/.

Examples include the interfacial polymerization method described in U.S. Pat.

In general, electron-donating colorless dyes are used alone or in combination as solvents (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, alkylated terphenyl, etc.).
(synthetic oils such as chlorinated paraffin; vegetable oils such as cotton oil and castor oil; animal oils; mineral oils and mixtures thereof)
After dissolving it in microcapsules,
A color forming agent sheet is obtained by coating it on a transparent or opaque smooth support such as paper, high-quality paper, plastic sheet, resin-coated paper, etc.

In addition, an electron-accepting compound alone or in combination with other electron-accepting compounds is dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and the electron-accepting compound is dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol.
By coating on a support such as resin-coated paper, a
Obtain a colorant sheet.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be used depend on the desired coating thickness, the form of the pressure-sensitive copying paper, the capsule manufacturing method, and other conditions, and may be adjusted as appropriate depending on the conditions. It is easy for one skilled in the art to determine this amount to use.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound have a concentration in the dispersion medium of 10 μ or less, preferably 3
It is used after being pulverized and dispersed to a particle size K of μ or less. As the dispersion medium, an aqueous solution of a water-soluble polymer having a concentration of about 10% or more is generally used, and the dispersion is carried out using a ball mill, a sand mill, a horizontal sand mill, a colloid mill, or the like.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is from /:10 to I:0. / is preferable,
Furthermore l:! and Koni 3 are particularly preferred. At that time, aromatic ether compounds such as JP-A-Sho! r-172
ri, same as '! An aromatic alkyl or substituted alkyl ether and/or an amide having a long chain alkyl group as disclosed in -17Or4A may be used in combination. Examples of such ether compounds include (endyloxynaphthalene, di-m-tolyloxyethane, β-phenoxyethoxyanisole, l-phenoxy-λ-p-ethylphenoxyethane, bis-β-(p-methoxyphenoxy ) ethyl ether, t-2'-me) diphenol ≠ "-
Ethyl-Φ diphenol siethane, /, 2-diphenoxyethane 7, /.

Gudiphenoxybutane, bis-β-(diphenoxy in p-eth)ethyl ether, l-phenoxyco p-
Chlorophenoxyethane%/l Corbis(β-phenoxyethoxy)benzene, l.

J-bis(β-phenoxyethoxy)benzene, l-μ
'-Methylphenoxy7-2-≠ -fluorophenoxynitane, l-phenoxy-J-p-naphthoxyphenylthioethane, /・, Corbis-p-methoxyphenylthioethane, l-tolyloxy-col-methoxyphenylthioethane, etc. It is preferable to use an ether of or a compound such as stearic acid amide, methylene bis stearamide, stearic acid aniside, behenic acid amide, stearic acid anilide, or stearyl urea. These are used in finely dispersed form at the same time as a colorless dye or at the same time as an electron-accepting compound. In particular, it is preferable to disperse the colorless dye at the same time from the viewpoint of preventing fogging. These usage amounts are
It is added in a weight ratio of 300% or less to the electron-accepting compound, particularly preferably 10% or more and less than 10% by weight.

Additives are added to the coating solution obtained in this way in order to meet the specific requirements.

Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder in order to prevent the recording head from becoming dirty during recording, and also to improve releasability from the head. For this purpose, fatty acids, metal soaps, etc. are added. Therefore, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, additives such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, and surfactants are used. is applied onto the support to constitute the recording material.

Specifically, pigments such as kaolin, calcined kaolin, Merck, zinc oxide, diatomaceous earth, calcium carbonate, aluminum hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, Micro/9 rune, urea-formalin filler, polyethylene particles, cellulose filler "4" with a particle size of 0°7 to 1)μ.

Examples of waxes include benzyl biphenyl, paraffin wax, calxoxy-modified wax, crystalline wax, polyethylene wax, and higher fatty acid esters such as benzyl insyloxybenzoate and octyl stearate.

Examples of metalstones include polyvalent metal salts of higher fatty acids, ie, zinc stearate, aluminum stearate, calcium stearate, zinc oleate, and the like.

As a hindered phenol, at least 2 or 4
A phenolic conductor in which one or more of the positions is substituted with a branched alkyl group is preferred.

For example, /, /-bis(-1methyl-derhydroxy-j-t-butylphenyl)methane 1 /1/, J-
) Lis(3-methyl-μmhydroxy-z-t-butyl phenyl)methane, bis(coffee)"0ki7-,?
-t-, thiruj-methylphenyl)methane, bis(comethyl-≠-hydroxy-!-1-butylphenyl)
Sulfy)”lf6ru.

As ultraviolet absorbers, cinnamic acid derivatives, incere f-
derivatives, benzotriazolylphenol derivatives, etc., such as butyl α-cyano-β-phenylcinnamate,
Examples include -benzotriazolylphenol, 0-benzotriazolyl-p-chlorophenol, O-benzotriazolyl-21 μm digtylphenol, and 0-incitriazolyl-p-chlorophenol. Among these, benzotriazole phenol derivatives are particularly preferred.

These materials are also detailed in the patents mentioned above.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxyzolobyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and imbutylene-anhydride. Examples include maleic acid copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin. In addition, water-resistant agents (gelling agents, cross-linking agents) are added to these binders for the purpose of imparting water resistance, and emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. You can also add

Furthermore, for the purpose of imparting chemical resistance to the surface of the coating layer, O, j~ consisting of a water-soluble polymer compound such as polyvinyl alcohol, hydroxyethyl starch or epoxy-modified polyacrylamide and a gelling agent (hardening agent) is added. A layer of about 2μ can also be provided.

The coating fluid is most commonly applied onto base paper, wood-free paper or synthetic paper, preferably neutral paper.

Generally, the coating amount is 2-/0 as solid content. / ?
About F12 is used.

When using it for thermal paper, please use OLS Co., 2.2rjr.
No. 1, same/101! Hiroshi, special public Akira! Various aspects described in λ-201≠2 etc. can be taken. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

The electrically conductive thermal paper is manufactured by the method described in, for example, ii' Japanese Patent Application Laid-open No. 3/3μ1 and JO-AT No. 30. Generally, a conductive layer is formed by coating a support such as paper with a coating liquid in which a conductive substance, a basic dye mainly composed of fluoran derivatives, and an electron-accepting compound are dispersed together with a binder, or by coating a conductive substance on the support. The electrically conductive thermal paper of the present invention is produced by applying thereon a coating liquid in which a colorless dye, an electron-accepting substance, and a binder are dispersed.

Note that the sensitivity can also be improved by using the thermofusible substance described above in combination.

For example, the photosensitive and pressure sensitive paper is made by Tokkai Sho! 7-/72136, etc. In general, photopolymerization initiators such as silver iodobromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives, and benzophenone conductors are combined with polyfunctional monomers such as polyallylates, poly(meth)acrylates, and poly(meth)acrylamides. The crosslinking agent is encapsulated in a synthetic resin wall capsule such as polyether urethane, polyurea, etc. together with a colorless dye and optionally a solvent. This method, which is developed by the present inventors, is colored by making use of the colorless dye in the unexposed area and bringing it into contact with a color developer after imagewise exposure.

(Examples of the Invention) Examples are shown below, but the present invention is not limited only to these examples.

Example 1 Each of co-anilino-3-methyl-6-N-ethyl-N-ynamylaminofluorane-1,2-anilino-3-chloro-t-diethylaminofluorane and 2P was dissolved in 3.5% polyvinyl alcohol Measurement tata%, degree of polymerization 1000) aqueous solution λ! The particles were dispersed into particles having an average particle diameter of 2 using a Tomatosu/Domil.

On the other hand, α,α′-his
-p-xylene lOf% copenzyl oxynaphthalene?
rt was dispersed with s% polyvinyl alcohol aqueous solution and 02 in a ball mill overnight. Furthermore, β-p-methoxyphenoxyethyloxysalicylic acid rt, zinc oxide 10f
3% polyvinyl alcohol aqueous solution! Disperse with Of in a ball mill all day and night. Furthermore, i,i,s-trisuco'-methyl-μ'-hydroxy-r'-t-butylphenylbutane 0,2 tf! % polyvinyl alcohol aqueous solution l! 2 and dispersed throughout the day and night.

After mixing this thoroughly, add Joshia kaolin ljt and fine particle silica 4? Add and disperse well to create a paraffin wax emulsion! A θ% dispersion liquid (Chukyo Yushi Cellosol #4A Cor) at was added to prepare a coating liquid.

The coating liquid is ≠! Fine calcilum carbonate having a basis weight of 97 m was coated on neutral paper coated with 8B as a binder so as to have a basis weight of 2 f/m2, and the solid content coating amount was z, 4.
It was applied so that the area was 17m2.

After drying for 1 minute at Go''c, a coated paper (A) was obtained by applying a super medium-yelender with linear pressure!O#W/B.

Coated paper requires heating energy of 3z m by facsimile machine.
When the color density was determined by heating with J 7mm,
0 on Macbeth reflection densitometer. riOtonacibisphenol A
It showed a similar degree of color development.

The obtained recording material had no fog during raw storage and had excellent stability over time.

On the other hand, the obtained colored images were clear black and showed good resistance to chemicals, water, sunlight, etc.

Example 2 fiKα instead of α,αl-bis(p-hydroxyphenylthio)-p-xylene used in Example 1.

A coating liquid was obtained by the same treatment using αI-bis(Hiro-hydroxyphenylthio)-〇-xylene.

When this coating liquid was applied based on the method of Example 1 and dried, it developed a clear black image and showed good resistance to chemicals, water, etc., and no decrease in powder density was observed over time. I couldn't.

As described above, by using the electron-accepting compound of the present invention, it was possible to obtain a recording material with excellent chemical resistance, water resistance, and stability against streaking of colored images.

Claims (1)

[Scope of Claims] A recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, characterized in that a compound represented by the following general formula (I) is used as the electron-accepting compound. Recording materials include mathematical formulas, chemical formulas, tables, etc. (I) In the above formula, R is a divalent group containing at least one aromatic ring,
R_1_ to_4 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an acyl group, a hydroxy group